Alkali-metal titanate and method of making same



Patented Jan. 8, 1929.

UNITED STATES I 1,697,929 PATENT OFFICE.

LONN IE W. RYAN, 0F NIAGARA FALLS, NEW YORK, ASSIGNOR TO TITANIUM PIGMEN'I' COMPANY, INC., OF NEW YORK, N. Y., A CORPORATION OF MAINE.

ALKALI-ME'IAL TITANA'I'E AND METHOD OF MAKING SAME.

No Drawing.

My invention relates to titanium compounds and methods for their economical manufacture which compounds have varied uses in the industrial art s. My invention provides more particularly an improved and more economical method for converting hydrated titanium oxygen compounds as metatitanic acid and titanium basic sulphate. into a titanium compound having novel characteristics and properties, more particularly its ready solubility in organic and dilute mineral acids. I

My invention is particularly useful in the manufacture of double salts of titanium and alkali metal such as, for example,titanium sodium tartrate, titanium sodium lactate,

titamum potassium oxalate, titanium sodium sulphate, etc'. Such invention is likewise equally useful in the manufacture of mixed salts such as, for example, those of tltanlc, oxalic and tartaric acids; and of titanic, oxalic and lactic acids, These salts are of commercialimportance and of great and extensive use in the arts, particularly in the leather and textile industries.

The ortho and meta-hydroxides of titanium, 'Ti (OH) 4 and TiO OH) sometimes called-ortho and meta-titanic acids, respectively, are generally believed to exist. But there is reason to 'think that the molecules of these two hydrates of titanic oxide may be very complex and only approximate to the composition represented by these formulae. The main distinguishing difference in behavior of the two is the solubility of the ortho form in strong organic acids and in dilute mineral acids, whereas the meta form is insoluble in these acids.

The ortho-titanic acid is obtained as a voluminous, white precipitate upon adding alkalimetal or ammonium hydroxide or carbonate to a cold solution of titanium chloride, resulting, When dried and calcmed, 1n very hard, horny and dense masses. The metatitanic acid may be obtained by various meth: ods; for example, by boiling an aqueous solution of titanic chloride. a

The United States Rossi and Barton Patcnts Nos. 1,196,029, 1,196,030 and 1,196,031

issued August 29, 1916, disclose how a basictitanic sulphate can be precipitated by diluting a titanic sulphate solution with water and thereafter boiling same. Such basic sul phate so produced is not soluble in dilute mineral acids nor in strong organic acids.

, conditions,

Application filed June 2, 1925. Serial Elm-84,478.

' Oneof the objects of my invention is,

among other-things, not to remove the SO radical, but to form a product or compound which is'readily soluble both in organic and in dilute mineral acids.

I have discovered that hydrated titanium oxygen compounds such as meta-titanic acid and titanium basic sulphate (the latter'being really a form of meta-titanic acid carrying a small omount of S0 may, under certain carbonate at a temperature below thepoint of fusion into a novel product or compound that is soluble in organic and dilute mineral acids, only or even less, of the theoretical amount of caustic alkali for formation of the alkali metal meta-titanate (M,TiO being required in my improved methods, and the temperature need not exceed 150 C.

I am aware-that it is known that meta titanic acid and titanium basic sulphate as be converted with a relatively small amount of caustic alkali or alkali metal well as certain ores of titanium such as rutile and ilmenite, may be rendered soluble in acids by heating to the point of fusion with a small amount of alkali. But such a process is carried out with the greatest difliculty owing chiefly to the corrosive action of molten alkali on furnace linings.-

To accomplish such conversion according to my improved methods, I mix the titanium compound with a small amount of alkali metal hydroxide or carbonate and a small amount of water and heat to a comparatively low temperature. It will be observed that in my process I am able to eliminate the obj ections to the older Well known fusion process. I use a small amount of the alkaline compound of an alkali metal and a tempera order of their effectiveness, as follows: potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate. The reaction goes most readily with potassium hydroxide and with the most difliculty with sodium carbonate.

Basic sulphates made by me have analyzed from 75% to.78% TiO from 7% to 10% S0 and from 12% to 17% combined water. These analyses correspond closely to the em pirical formula (TiO ,,.SO .10H O.

Such a formula represents 7 5.47% T iO 7.55% S0 and 10.98% H,,().

When converting such a titanium compound to a soluble product by usingpotassium hydroxide (KOI-I) for meta-titanate formation, I assume that the reaction goes the TiO,' content is as follows (TiO 1011 0 2OKOH= The theoretical ratio of the titanium oxide, TiO contained .in the basic sulphate.

T10 ,0.SO 3.10H2O I to potassium hydroxide KOH is 80'to 112.

The presence of the S0 radical causes the formation of one mole of K SO and one mole of the acid titanate, K Ti O If a sufficient I excess of KOH is used to-t-ake care of the S0 radical, I assume that the reaction takes place as follows:

not contain an acid radicalsuch as S0,, to a soluble product, I assume that the reaction goes as follows:

TiO (OH) 2 2KOH= K no, 2H,,Q

tween titanium basic sulphate and the potas-' sium carbonate are approximated by the following equations:

and I The reactions between metal titanic acid and- TiO(OH),+K CO,=K,TiO, +11 0 +00,

and 1 The following are examples of how my invention can be' carried into practical effect,

' but the invention is not to be con fined to these examples.

Ewample 1.Metatitanic acid or basic titanic sulphate prepared in any manner whatsoever, is made into apaste with water so that about 30%. If the basic sulphate has been used, 1600 pounds of 90% potassium hydroxide is slowly added to 3300 pounds of the paste, containing about 1000 pounds of TiO,, and stirring with an agitator, by tumbling in a barrel or by any suitable method. The

amount of potassium hydroxide used is equal to 1.6 times the weight of the titanium oxide contained in the basic sulphate or'the metatitanic acid.- This amount of- KOII is theothe materials mixed by retical for, the conversion of all the titanium to the metatitanate and the S0, to K,,SO,. I prefer using a shallow steel tank and stirring with a steel agitator as the potassium hydroxide'is added. Heat is then applied for l from 1 to 4 hours depending upon the temperature. Ihave found subjecting to a temperature of to 200, 0., ordinarily not exceeding 140 C. for from 2 to 3 hours to be a convenient, practical operation. It is not necessary to stir after the potassium compound has been thoroughly mixed in.

E wample .2.Moist meta-titanic acid or titanium basic sulphate containing about 1000 lbs. TiO is'mix'ed with 2000 lbs. of potassium carbonate. After thorough mixing the material is heated at a temperature of about 200 C. for from three to four hours. At the end of this time reaction has taken lace, the final product being essentially TiO' soluble in organic and dilute mineral acids and in mixtures of acids. It may then be dissolved in a similar manner as hereinafter described in Example 3.

The product formed in any case is an essentially white, minutely crystalline powder which is only slightly, ifat all, hygroscopic. ,The specific gravity of the dry material ranges between 2.3 and 2.9 depending upon the proportion and kind of alkali used. There is no difference in the products made from the basic sulphate and the "hydroxide (metatitanic acid), except that that made from the basic sulphate contains a small amount of alkali sul hate. The composition is represented by 518 formula K TiO or Na TiO when enough alkali metal hydroxide or carbonate. is used for the formation of these compounds. If less of the alkali metal compound is-used the product is a. mixture of the above with K Ti O or Na Ti O or if a sufliciently small amount of the alkali metal compound is used (see equations) the product is entirely K,,Ti,O or Na Ti O It is to be understood that the above formulas represent ap' roximately the true compositions, the pro ability being that the molecules are very complex. If the basic sulphate is'used as a starting material, the product always carries a small amount of K SO, or N 21 80 In practice it is not necessary to drive 01f all the water, therefore the product may also carrya small amount of water.

Such alkali metal compound, or product is soluble in any number of different acids and mixtures of acids. It may be dissolved direct in the acid, the salt of which it is desired to make; or it may be hydrolyzedwith water, some of the alkali metal washedout and the residue is then dissolved in the acid. The following example will disclose how this compound is dissolved in oxalic acid to produce titanium potassium oxalate.

Example 3.About 3200 lbs. of oxalic acid are dissolved in 2000 gallons of water and the temperature brought to about 80 C. The potassium meta-titanate, either dry or in a moist condition, is now slowly added with continuous stirring and the temperature is maintained at about 80 C. There is this immediately formed in solution by double decomposition, titanium potassium oxalate-K OTi(C O which after filtering from the slight amount of insoluble material may be crystallized in any known manner. The potassium sulphate present is not detrimental and is eliminated in the crystalliza tion of the oxalate. The reaction goes ac cording to the following equation:

The foregoing detailed description gives a 'clear understanding of my invention but no limitations should be deduced therefrom, as-

- tanium oxygen compounds with an alkaline acid substance with an alkaline compound of an alkali metal to form an alkali metal meta titanate, and heating to a temperature below the fusion point. 4

4. The method of making a titanium compound which comprises mixing hydrated titanium oxygen compounds containing an acid substance with an alkaline compound of potassium to form a potassium meta titanate, and heating to a temperature below the fusion point.

5. The method of making a titanium compound which comprises mixing hydrated titanium oxygen compounds contaimngsulphuric anhydrid with an alkaline compound of an alkali metal to form an alkali metal meta titanate, and heating to a temperature below the fusion point. a

6. The method of making a titanium compound which comprises mixing hydrated titanium oxygen compounds containing sulphuric anhydrid with an alkaline compound of potassium to form a potassium meta titanate, and heating to a temperature below the fusion point.

As a new article, the hereindescribed I titanium compound characterized as being a calcined product, of s ecific-gravity 2.3 to 2.9, in the form of a ne, minutely crystally white in color, containing a preponderance of titanic oxide, and soluble in organic and dilute mineral acids.

8. As a new article, the hereindescribcd titanium compound characterized as being a calcined product, of s ecific gravity 2.3 to 2.9, in the form of'a ne, minutely crystalline powder, slightly hygroscopic, essentialance of titanic oxide with a small amount of alkali metal sulphate, and soluble in organicand dilute mineral acids.

LON NIE W. RYAN.

. line powder, slightly hydroscopic, essential- 1y white in color, containing a preponder- 

